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By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T'K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall' who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,' consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By C. F. Knutson, Martin Felsenthal, J. D. Lung, J. D. Sudbury

This paper has been written to summarize the laboratory and field studies leading to injection of Pacific Ocean water into the Third Grubb formation. Laboratory tests for studying the permeabilities of cores to Pacific Ocean water are described. Resu1ts of these tests showed that the water could be successfully injected if it is chertzically stable, sterile, and properly filtered. Clay swelling was shown to be a comparatively minor factor in permeability reduction. Studies leading to development of an economical system for properly conditioning the ocean water are discussed. It was necessary to control pH, calcium carbonate deposition, bacterial growth, iron solubility. oxygen, and suspended .solids. A relatively simple system combining the use of sulifur dioxide, a quaternary rlmmonium chloride, and filtration was shown to adeqrrately control all these factors. This combination has not previozrsly been used as a water treating technique. Evaluation tests of the water conditioning system prior to injection are described, and results of such tests are presented. Control measures needed to insure a continusously adequate water treatment are reviewed. INTRODUCTION The utilization of sea water for waterflooding has only recently been attempted. Knowledge of treating requirements has been limited, and in most cases no water treating has been done. Prior to the initiation of the Third Grubb zone pilot water flood at Ventura, Calif.,1,2 extensive laboratory research was done in an effort to define the treatment necessary to provide a suitable injection fluid. Close coordination and cooperation between field and research personnel were found to be the foremost requisites in developing the most economical and practical method for treating ocean water. LABORATORY STUDIES Plugging Tendencies of Untreated Ocean Water A program of laboratory studies was initiated for the purpose of evaluating whether ocean water could be injected into the formation for prolonged periods of time without causing plugging of the pore spaces of the formation. Because of the fairly low permeability of the formation (averaging about 40 md), it was realized from the outset that a water of exceptionally high quality was needed. Ocean water used in the laboratory studies was carefully filtered through ultrafine fritted glass filters, having nominal maximum pore sizes of 1.4 microns. Permeability tests were then performed on representative core material from the formation. It soon became apparent in these tests that filtration alone was not a sufficient treatment for the ocean water. Prolonged injection of the filtered water caused rapid plugging of the core samples. The permeability decline of a typical sample is illustrated by Curve A in Fig. 1. The several factors which can contribute to this plugging tendency are briefly reviewed below: Interaction with Formation Clays An evaluation of clay swelling effects on liquid permeability was made using core samples from the Grubb formation. An oil was chosen for determining the reference liquid permeability because it would not tend to react with any clays that might be present in the formation. The samples were then extracted, dried, and resat-urated with either treated ocean water, formation water, or fresh water. Permeabilities to the various waters were then determined. Results of this test series are summarized in Fig. 7. The difference between the oil permeability and water

Jan 1, 1957

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By U. N. Bhrany, J. H. Brown

The specifications of particle size and the size analyses of fine particulate materials are commonly presented without reference to the method of analysis. A review of the various sizing methods showed that not only numerous sources of error but also different definitions of size are inherent in the different methods of analysis. To demonstrate the magnitude of the differences, the size distribution of finely crushed quartz was determined by several methods and a critical comparison of the data was made. The experimental results show that appreciably different sizes may be indicated for one material depending on the method of analysis used. However, because the shape of the size-distribution curves determined by almost all methods was constant, a simple method of correlating the data can be adopted. Conversion factors, by which size measurements obtained by the various methods can be expressed in terms of screen sizes, are presented as one method of correlating the results. The size analysis and size specification for lump rock and particulate materials are commonly determined with sieves. With this technique, a readily reproducible measure of size can be obtained merely by duplicating the sieve and the method of sizing. For coarse materials, such as lumps of rock, this technique is simple and effective; and the effects of properties of the material such as shape can be readily understood. When very small particles are measured, however, problems arise. Small sieves are difficult to construct and maintain, and size separations become sensitive to the analytical procedure. For these difficult sieve sizes and for still smaller particles, other sizing techniques employing, for example, sedimentation, light extinction, and microscopy are available. Because these various techniques employ different size-dependent responses to establish size, it is appropriate to examine them and the results they yield to determine their relationships and their limitations. The 'size' of a lump of rock is not an absolute quantity, but rather a defined one. With sieves, for example, the size is defined by the screen aperture and no reference is made to the actual shape of the particle, yet only in the case of a regular body, such as a sphere, can the sieve size be related to the shape. With sieves only two dimensions of a particle can be suggested, for the sieve makes no allowance for the length of the particle passing through an aperture. Similarly, the size of a particle as measured by a microscopic technique need bear no relationship to the size as measured by sieves, although the two measurements may be related statistically. In fact, all size measurements are not only defined quantities, but the measurement actually used is an average that is controlled by the technique employed and, hopefully, reflects the property in question of the material of interest. Many papers have been presented that illustrate the accuracy of the various sizing methods, present the advantages of certain methods for certain applications, and describe the principles and technical backgrounds of the various methods. No attempt will be made in the present paper to review this work in detail. The purpose of the present paper is to examine the limitations of the various sizing methods, and to demonstrate experimentally the relationships between the sizes as determined by the various methods of analysis. It is hoped that by recognition of these limitations and relationships, errors in size specification and size interpretation will be avoided. REVIEW OF SIZING METHODS In specifying the size of a material, not only the data but also the method of measurement must be stated. For example, the size of the lump might be specified as its total volume, as its weight, as its maximum dimension, or as its minimum cross section; any one definition might be completely satisfactory for one problem, but not for another. In practice, size analyses follow four basic approaches and fortunately, the conditions that restrict each approach are known. These major methods include: 1) screen analysis, 2) direct measurement of particle dimensions, 3) determination of equivalent spherical size in response to fluid flow, and 4) specific surface determination. Each of these techniques has several variations and some new techniques are also available, but the limitations of the basic techniques are sufficient to permit at least a preliminary

Jan 1, 1962

By William H. Spice

The year 1942 in the South Central Texas area was marked by a sharp curtailment of exploratory drilling as compared with the past several years. In the 33 counties that compose this district, 17 of which are nonproducing counties, only 51 exploratory wells were drilled during the year 1942. This compares with 118 exploratory wells drilled during 1941, or a decrease of more than 50 per cent. At the end of the year 10 active exploratory wells were drilling in this area, as against 19 being drilled at the end of 1941. Of the exploratory wells drilled, two brought in oil wells and were new field discoveries and one was a gas well extending a recently discovered shallow gas area in the western part of the district. This compares with five new oil fields, one new . gas field and two extension wells drilled in 1941. Both new field discoveries were small and in areas outside of the general trend of the main producing horizon of the district in Edwards limestone: One new field, the Imogene, in Atascosa County, is a deep Edwards limestone prospect at 7500 ft., and the other new field, the Poth, in Wilson County, is a sSEa110w Wilcox (Eocene) prospect at 4000 ft. Subsequent drilling in each field to the end of I942 has proved disappointing. There were no new discoveries along the old Balcones fault-line trend, although 35 of the exploratory wells were drilled in counties along this trend. Approximately 38 wells were drilled in or adjacent to the proven fields of the district, of which 18 were oil wells, 2 were gas wells and 17 were dry holes. The district produced 6,186,178 bbl. of oil during 1942, which was a 7 per cent decrease under production for 1941. Approximately 4,961,000 bbl. of this total production, a slight increase over 1941, was produced by the four Edwards-limestone fields, Luling, Branyon, Salt Flat and Darst Creek, and the rest of the production came from the other 42 active fields in the district. During the year, 20 new producing wells were completed and 221 wells were abandoned in the producing fields. This alarming excess rate of abandonment~ over completions will be further reflected undoubtedly by a further decreased rate of 1943 production under 1942. Two active fields in the district in which more than one producing well was completed during the year were Bee Creek and Washburn. The majority of exploratory work in the district was confined to areas along the Wilcox trend, with a certain amount in progress along the deeper Edwards limestone trend. The successful completion of sevemi wells in the Washburn field from multiple sands in the Lower Wilcor (Eocene) has stimulated exploratory work along this trend, while the completion of a small well in the Imogene field from the Edwards limestone at 7500 ft. has renewed interest in this horizon at depths greater than generally are producing in the district. New Fields ounty. ble Oil and Refining Company's No. I

Jan 1, 1943

By E. Rudy, St. Windisch

The only complete phase diagram investigation of the Ti-W system is by Maykuth and coworkers,&apos; Fig. 1. Although previous work by Gonser2 indicated complete miscibility, later investigations3°5 essentially confirmed the diagram depicted in Fig. 1. The present study was undertaken because preliminary results on metal-rich ternary Ti-W-C alloys indicated complete solid solubility between 0 titanium and tungsten at temperatures above 1300°C—in contradiction to the presently accepted diagram. The powdered elements, as well as crystal bar titanium and tungsten sheet, were used in the preparation of the experimental alloys. The iodide titanium, obtained from Foote Mineral Co., Exton, Pa., had a total impurity content of less than 410 ppm, of which 150 ppm were interstitials (H, O, N, C). The overall purity of the titanium powder (Var-Lac-Oid Chemical Co., New York) was better than 99.7 pct. Major contaminants, in ppm, included: 0, 800; N, 10; H, 1500; Fe + Co + Ni + Cu + Zn, 50; C1, 200. The measured lattice parameters of the titanium were a = 2.94A and c = 4.68,A. The tungsten sheet and the tungsten powder (Wah Chang Corp., Albany, Ore.) contained the following impurities (in ppm, values in parentheses refer to the sheet tungsten): Mo, 50 (70); 0, 140 (110); Fe, 20 (60); Ni, 20 (not determined); N, 110 (not determined); sum of other impurities, <60 (<100). Samples from the iodide titanium bar stock and from tungsten sheet were prepared by repeated melting of the chipped materials in a nonconsumable electrode arc furnace under high-purity helium. The melted alloys were heavily cored, and homogeneity of the alloys could only be achieved after prolonged heat treatments at subsolidus temperatures. The majority of the alloys were therefore prepared by cold compacting the well-mixed powders in steel dies and pre-homogenizing the compacts for 6 hr at 1300°C in a tungsten-element furnace. The vacuum was better than 10"6 Torr, but for additional protection the sample container was wrapped in zirconium foil. Both preparation methods led to identical results. The measurements of the solidus temperatures were carried oat in the Pirani-type furnace described in a previous paper.6 Incipient melting in alloys containing between 20 and 90 at. pct W was rather difficult to detect visually, and therefore a photoelectric transducer system7 was employed to indicate the phase change. For the investigation of the solid-state equilibria, the specimens were first homogenized for 2 hr at slightly subsolidus temperatures in the Pirani fur- nace and then reequilibrated at, and rapidly cooled (-100°C per sec) from, the selected equilibrium temperatures. After the runs, the alloys were analyzed microscopically and by X-ray diffraction. With the exception of spot checks for oxygen and nitrogen in processed alloys, no other chemical analyses were performed. However, as the weight changes of the alloys during processing were within 0.05 pct and the lattice parameters of indeqendently prepared alloy series agreed within 0.0015A, it is reasonable to assume that no significant concentration shifts with respect to the nominal compositions had occurred. The measured solidus temperatures, shown together with literature data in Fig. 2, ascend smoothly from

Jan 1, 1969

By William H. Spice

The year 1942 in the South Central Texas area was marked by a sharp curtailment of exploratory drilling as compared with the past several years. In the 33 counties that compose this district, 17 of which are nonproducing counties, only 51 exploratory wells were drilled during the year 1942. This compares with 118 exploratory wells drilled during 1941, or a decrease of more than 50 per cent. At the end of the year 10 active exploratory wells were drilling in this area, as against 19 being drilled at the end of 1941. Of the exploratory wells drilled, two brought in oil wells and were new field discoveries and one was a gas well extending a recently discovered shallow gas area in the western part of the district. This compares with five new oil fields, one new . gas field and two extension wells drilled in 1941. Both new field discoveries were small and in areas outside of the general trend of the main producing horizon of the district in Edwards limestone: One new field, the Imogene, in Atascosa County, is a deep Edwards limestone prospect at 7500 ft., and the other new field, the Poth, in Wilson County, is a sSEa110w Wilcox (Eocene) prospect at 4000 ft. Subsequent drilling in each field to the end of I942 has proved disappointing. There were no new discoveries along the old Balcones fault-line trend, although 35 of the exploratory wells were drilled in counties along this trend. Approximately 38 wells were drilled in or adjacent to the proven fields of the district, of which 18 were oil wells, 2 were gas wells and 17 were dry holes. The district produced 6,186,178 bbl. of oil during 1942, which was a 7 per cent decrease under production for 1941. Approximately 4,961,000 bbl. of this total production, a slight increase over 1941, was produced by the four Edwards-limestone fields, Luling, Branyon, Salt Flat and Darst Creek, and the rest of the production came from the other 42 active fields in the district. During the year, 20 new producing wells were completed and 221 wells were abandoned in the producing fields. This alarming excess rate of abandonment~ over completions will be further reflected undoubtedly by a further decreased rate of 1943 production under 1942. Two active fields in the district in which more than one producing well was completed during the year were Bee Creek and Washburn. The majority of exploratory work in the district was confined to areas along the Wilcox trend, with a certain amount in progress along the deeper Edwards limestone trend. The successful completion of sevemi wells in the Washburn field from multiple sands in the Lower Wilcor (Eocene) has stimulated exploratory work along this trend, while the completion of a small well in the Imogene field from the Edwards limestone at 7500 ft. has renewed interest in this horizon at depths greater than generally are producing in the district. New Fields ounty. ble Oil and Refining Company&apos;s No. I

Jan 1, 1943

By H. J. Beach, W. C. Goins

The laboratory development and field use of oil well cement compositions* with high resistance to drilling mud contamination are described. Resistance is obtained by adding a I-lb mixture composed of three parts paraformaldehyde to two parts sodium chromate tetra-hydrate for each sack of cement. This mixture neutralizes the cement-retarding properties of quebracho and other tannins, starch, sodium carboxymethylcellu-lose, Ignite, and monovalent salts of lignosulfonic acid. The retarding properties of calcium lignosulfonate are unaffected. The decontaminating mixture may be used in common cement (designated Type I by ASTM specifica-tions,&apos; Class A by API Std. 10A2) or in a slow set slurry prepared from common cement by addition of calcium lignosulfonate. No changes in slurry viscosities or thickening times are caused by the protecting reagents. The method has been used in 185 field jobs where an improved success ratio has been obtained in plug setting. INTRODUCTION Field experience and laboratory investigations have established contamination by drilling mud as a major factor in oil well cement failures. During 1955, 12 attempts were required to set six open-hole cement plugs in the Timbalier Bay field, La. Eighteen to 30 hours elapsed between placing and testing the plugs in preparation for sidetracking operations. Considerations of rig time expense required immediate resetting where soft cement was drilled after a reasonable waiting period. Sea water drilling mud was used in each well and daily additions of thinners, usually lignites, had been required. Sodium carboxymethylcellulose had been added regularly to control fluid loss. The 50 per cent plug failures were attributed primarily to contamination by the mud. Similar experiences can be found in other fields along the Texas and Louisiana coasts where drilling muds normally contain large quantities of organic treating materials. Cement contamination was the subject of a survey by the Mid-Continent District Study Committee on Cementing Practices and Testing of Oil-Well Cements of the API.3 Data collected from member laboratories and released in Sept., 1951, reported the effects of a number of drilling mud treating chemicals on cement. The study revealed that many of the additives, notably the organic materials in relatively small quantities, had marked effects on the properties of cements tested. Severe losses in strength and erratic thickening time resulted from small additions of mud treating chemicals such as quebracho, starch, sodium carboxymethylcellulose, and lignite. The report included no recommendations of methods for overcoming the problem. One investigation of the contamination problem reported the successful use of activated charcoal in setting cement plugs after conventional slurries had failed.4,5 The investigation indicated that an optimum concentration of 5 per cent activated charcoal was effective in combating contamination from 16.7 volume per cent of treated mud. Laboratory and field muds were included in tests and contained varied quantities of ode or more of the following: quebracho, caustic, starch, lime, and calcium lignosulfonate. The function of the charcoal appears to be physical, removing the organic materials by adsorption. The method may be employed in API Class A or Class D (unretarded slow set) cements. The chemical approach presented here is based on

Jan 1, 1958

By L. R. Plitt, E. O. Lilge

Tests carried out with both kaolin and silica slurries show that flocculants of the polyacrylamide type can be used to improve the thickening performance of hydrocyclones. This thickening improvement demonstrates that contrary to previously held theories, flocs can be formed which are capable of resisting the shear forces in a hydrocyclone. For the 1.25-in.-diam cyclone used, optimum thickening occurs when the flocculant solution is injected into the slurry stream at or near the feed inlet. Hydrocyclones offer many distinct advantages over gravity thickeners. These advantages include simplicity, low initial and operating costs, small space requirements, and flexibility of operation. In spite of these advantages hydrocyclones have not been widely used as thickeners. The main reason for their lack of application is that hydrocyclones are unable to efficiently remove semicolloidal particles (less than 5 microns) from the suspending solution. In gravity thickeners, the fine particles can be induced to form particle aggregates, or flocs, which have the settling characteristics of large particles. In the hydrocyclone, however, it was always assumed that the existence of shear would prevent the formation of flocs.1-3 Thus, if no floc structure is retained, the thickening hydrocyclone must be designed so that its separation size is below the size of the smallest particle to be recovered. To obtain a very small separation size requires the formation of very high centrifugal forces, which necessitates the use of small-diameter cyclones. Small hydrocyclones have, in turn, very low throughput capacities which render them impractical for many industrial thickening applications. Thus, if the effects of flocculation cannot be utilized, the usefulness of hydrocyclones as thickeners remains limited to pulps which contain no very fine particles. It is well established that most substances acquire a surface electric charge when brought into contact with an aqueous medium. The repulsive interactions between similarly charged particles act to prevent flocculation. One method of flocculating a dispersion is to neutralize the repulsive surface charges by the addition of an electrolyte. The reduction of the electrostatic surface charge (Zeta potential) then permits the universal van der Waals attractive forces to operate between the atoms of the various particles and form particle aggregates. The lime additions used by thickener operators promotes flocculation by this mechanism. A second method of flocculating a dispersion is by the addition of long-chain macromolecules. In this case flocculation is brought about by a bridging mechanism in which the molecules are adsorbed with part of their length on two or more particles, thus forming a molecular bridge between the particles.4,5 The molecules also form bridges between themselves when a single particle is bonded to several polymer molecules. The type of bonding between the flocculant molecule and the particle may be hydrogen bonding, chemical bonding, or electrolytic attraction.6 The flour and glue which are used as thickener additives are believed to promote flocculation in this manner. In the past decade synthetic long-chain polymers with extremely high flocculating capabilities have been developed. The flocs formed by these new polymeric flocculants are larger and more shear-resistant than those formed by the presence of electrolytes.7 The advent of these flocculants raises the question: Are the flocs formed by these synthetic polymers stable enough to resist the liquid shearing forces in a hydrocyclone? The investigations reported in this paper were carried out in order to provide some answers to this question. EXPERIMENTAL WORK For the bulk of the test work a 5% slurry of commercially available kaolin with an average particle size of 5 microns was used. An initial evaluation of the available flocculants was carried out to determine which flocculant formed the most shear-resistant flocs. A combination of the techniques used by Healy7 and Booth8 was used for this purpose. This initial study revealed that the neutral high-molecular weight polyacrylamides produced the most shear-resistant flocs. One of these flocculants, Separan MGL*, was selected and then used for all the hydrocyclone tests. The flocculant was dissolved in water and added to the hydrocyclone as a dilute solution.

Jan 1, 1968

By J. W. Leonard, B. A. Donahue

A method is described for incorporating coal petrography into mining and preparation plant quality control based on conventional analyses. Complete analyses are made of each of the uniform and relatively distinct petrographic bands in a coal face. With this information it is possible to develop petrographic standardization curves. These curves permit diverse coal characteristics to be rapidly monitored by application of a few standard coal tests. Single seam quality control is discussed in this paper. Inquiries continue to be made about coal petrography, and specifically, about whether coal petrography should be applied more extensively in the coal industry. Coal petrography is the study of the distinct physical, optical, and chemical increments which make up the organic rock mixture which we know as coal. Petrography can be applied by any coal company or at any coal mine where conventional coal analytical facilities are available and where additional resources can be allocated for an increased number of determinations. This first paper of a two part series includes (1) a proposed conventional approach to single seam petrography based on the development of petrographic standardization graphs and (2) some informative and supplemental interrelationships involving coal characteristics developed as a result of this research. In the second part of this series, to be published at a later date, those petrographic characteristics of bands taken from many different coal seams located over wide geographic areas which can be closely related to each other will be considered. These findings will be examined looking toward the development of a comprehensive, conventional approach to coal petrography which can be used as a common basis for multi-rank petrographic standardization graphs. Implicit to the understanding of coal petrography is the well established fact1,2 that the individual analyses of distinct petrographic bands often differ widely from the average analysis which is used to characterize a whole coal seam. In fact, a distinct and minor banded increment of coal in a high volatile seam may actually be a medium or low volatile coal with an analysis similar to the average analyses of seams located in distant coal fields. During the mining of coal, much degradation is caused which tends to randomly scatter coal bands. The degraded, scattered, and physically separated constituents of distinct petrographic bands are processed side by side in the coal preparation plant as distinct petrographic fractions with particles grouped according to a narrow size range (which derives in part from common hardness), specific gravity, and-or surface chemistry. Tile data obtained from numerous analyses made on each of the bands of any given coal seam, although diverse, can be readily interrelated. Indeed, these interrelationships can be developed into a series of nomographs or petrographic standardization graphs to serve as a basis for developing a conventional petrographic* program. Thus, by analyzing one property (for example, ash) of a selected petrographic fraction collected or separated from the flow of coal in a preparation plant, it should be possible to estimate the other physical, chemical, and thermal properties of this fraction by referring to the petrographic standardization graphs. It follows that any or all petrographic fractions in the total coal flow originating from a single coal seam can be rapidly monitored for many properties on the basis of a single analysis run on each fraction. In recent years coal petrographic research has concentrated heavily on that phase of this work which involves microscopic reflectance measurements made at many minute and selected points on a coal briquette surface.3,4 Thus, the percentage of the total number of reflectance measurements that fall into each of a consecutive series of arbitrarily chosen reflectance classes are used to characterize coal. This procedure is analagous to using the face of a coal briquette to represent the reflectance characteristics present at the face of a coal seam. Moreover, by analyzing petrographic fractions of known and uniform optical properties it is possible to closely relate reflectance to other coal characteristics. For example, reflectance has long been known to be related to such

Jan 1, 1968

Sec. 1. This Division shall be known as the Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers. Sec. 2. The object of the Division shall be to furnish a medium of cooperation between those interested in the metallurgy, fabrication and uses of the nonferrous metals and their alloys; to represent the A. I. M. E. in so far as nonferrous metallurgy is concerned, within the rights given in A. I. M. E. By-law XI., Sec. 1, and not inconsistent with the Constitution and By-laws of the A. I. M. E.; to hold meetings for social intercourse and the discussion of nonferrous metallurgy; to stimulate the writing, presentation and discussion of papers of high quality on nonferrous metallurgy; to reject or accept such papers for presentation before meetings of the Division. Article II—MembeRs Sec. 1. Any Member, Associate, or Junior Associate of the A. I. M. E. in good standing may become a Member, Associate or Junior Associate of this Division upon registering in writing a desire so to do, but without additional dues. Sec. 2. But no one who has been continuously indebted to the A. I. M. E. or to this Division for more than three months shall be entitled to vote or to receive publications to which, as a member of the Division, he would be entitled. Article III—Funds Sec. 1. The expenditure of the funds reccived by the Division shall be authorized by the Executive Committee of the Division. Article IV—Meetings Sec. 1. The Division shall meet at the same time and place as the annual meeting of the A. I. M. E., and at such other times and places as may be determined by the Executive Committee subject to the approval of the Board of Directors of the A. I. M. E. Sec. 2. The annual business meeting for election of officers shall be held within a few days before or after the annual business meeting of the A. I. M. E. Sec. 3. At any meeting of the Division for which notice has been sent to the members of the Division through the regular mail at least one month in advance, a business meeting may be convened by order of the Executive Committee, and any routine business transacted not inconsistent with these By-laws or with the Constitution or By-laws of the A. I. M. E. Sec. 4. For the transaction of business, the presence of a quorum of not less than 25 members of the Division shall be necessary. Article V—Officers and Government Sec. 1. The officers of the Division shall consist of a Chairman, two Vice-chairInen, Secretary and Treasurer. The office of Secretary and Treasurer may be combined in one person, if desired by the Executive Committee. Sec. 2. The government of the affairs of the Division shall rest in an Executive Committee, in so far as is consistent with the By-laws of the Division and the Constitution and By-laws of the A. I. M. E. Institute of Metals Divisiori

Jan 1, 1931

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada&apos;s Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada&apos;s experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By O. N. Carlson, H. A. Wilhelm, J. M. Dickinson

On the basis of microscopic studies, melting-point observations, and X-ray analyses, a phase diagram is proposed for the Cb-V system. A complete series of solid solutions is formed with a minimum in the solidus at 1810°C near 35 wt pct Cb. No compounds or intermediate phases were found in the system above 650°C. THERE is an ever increasing need for better structural metals and alloys for use in nuclear reactors. In addition to the normal properties of engineering structural materials, such as high temperature strength, resistance to corrosion, and fabric-abil~ty, the nuclear properties of the material must be considered. In a nuclear reactor it is important to conserve neutrons, so a material which removes these neutrons from the reaction excessively is considered to have unfavorable nuclear properties. In nuclear-reactor design the engineer must have nuclear as well as other data available on alloys in order to make a wise selection of materials. Due to the fact that many of the common structural materials have undesirable nuclear properties, it is vital that new alloys of metals having more favorable nuclear properties be investigated. Columbium and vanadium are both high melting metals, both exhibit resistance to chemical attack, and no great difficulty is encountered in fabricating them into desired shapes. With proper treatment both metals can be cold rolled extensively without failure. In addition they have desirable nuclear properties for certain types of reactors. Therefore, the alloys of columbium and vanadium should be of interest in the atomic energy program. Since an alloy-development program is enhanced by a knowledge of the phase equilibria of the components, this investigation was undertaken to establish the phase diagram for the Cb-V system. According to the Hume-Rothery rules for alloying,&apos; the chemical similarity, crystal structure, and atomic-size factor are favorable for a complete series of solid solutions for this system. Both elements are in the same family of group V of the periodic table and thus are quite similar chemically. The crystal structures of columbium and vanadium are compatible for extensive solid solubility, since both have body-centered-cubic structures. The atomic diameters of columbium and vanadium are 2.85 and 2.62Å, respectively. This difference of slightly more than 8 pct is well within the 15 pct maximum difference allowed for extensive solid solubility. Experimental Procedures Source of Materials: Columbium powder and sheet trimmings were obtained from the Fansteel Metallurgical Corp. According to the manufacturer the metal contains less than 1 pct impurity. An analysis of the metal showed approximately 1800 ppm C in the powder while the sheet trimmings contained less than 500 ppm C. Spectrographic analysis showed minor amounts of Ca, Cr, Fe, Mn, Si, Ti, V, and Zr in both forms of the columbium. No commercial source of vanadium having the ductility and purity desired was available to the authors at the beginning of this investigation. As a result, all of the vanadium used in this study was prepared by the bomb reduction of vanadium pen-toxide with calcium employing the method reported by Long.&apos; Yields of massive vanadium normally were about 80 pct. Chemical analysis of the vanadium prepared in this manner showed the presence of 200 to 500 ppm N and 800 to 1000 ppm C. Minor amounts of Ca, Fe, Mn, Si, Zr, Cr, and Cb were detected by spectrographic analysis. This vanadium metal was ductile and was cold rolled into 5 mil sheet. Annealing was not necessary during this rolling and the metal retained its cold-rolling characteristic after are-melting. Preparation of Alloys: The Cb-V alloys were prepared by melting pieces of vanadium sheet togethel-with columbium in the form of sheet or pellets of powder. The melting was carried out under argon in conventional arc-melting equipment employing a tungsten electrode and a water-cooled copper crucible. Each alloy was remelted three or four times, inverting the alloy after each melting in order to assure complete mixing. Alloys normally were obtained as round flat disks, weighed approximately 70 grams, and had roughly the shape of a disk 1 1/2 in. in diameter and 1/4 in. thick. Half of each alloy

Jan 1, 1955

By C. S. Matthews, H. C. Lefkovits

Drilling progress is often delayed by sticking of the drill string. The development of preventive and remedial methods has been hampered by incomplete understanding of the sticking mechanism. A recent lahorntory investigation hns indicated that one type of sticking may be attributed to the difference in pressure between the borehole and formation. This paper shows, by means of soil mechanics, that the primary cause for differential pressure sticking is cessation of pipe movement, whereas diflerential pressre and stanrtding time determine the severity of the sticking. The analysis stresses the importance of using low-weight muds with low solids content and low water loss to alleviate diflerential pressure sticking and describes why packed hole drilling, long strings of drill collars, and a large deviation from the vertical are conducive to sticking. Finally, preventrve and remedial methods ore evaluated, and a theory is presented on the release of stuck pipe by spotting oil. INTRODUCTION Since drilling with long strings of oversize drill collars has become standard practice in many areas, the incidence and severity of the stuck pipe problem has increased. It has been noticed that in the majority of these cases the sticking could not possibly be attributed to key seating or caving of shales. It appeared that, due to the differential pressure between the mud column and the formation fluid, the collars were pressed into the wall and so became "wall stuck". Points to note about differential pressure sticking are: (1) sticking is restricted to the drill collars, (2) the collars become stuck opposite a permeable formation, (3) the sticking occurs after an interruption of pipe movement, (4) circulation, if interrupted, can be restarted after the sticking is noticed, and (5) no large amounts of cuttings are circulated out after restarting circulation. Helmick and Longleyl investigated pipe sticking by differential pressure in the laboratory and found an empirical relationship between the differential pressure, the sticking time and the required pull-out force. In this paper an explanation of the mechanism is given based on Terzaghi&apos;s theory of clay consolidation. A qualitative description is given in the following paragraphs while the derivation of fonnulas is given in Appendices. This paper is a first attempt to explain pressure differential sticking and many points will require additional theoretical and practical investigation before the problem can be fully understood. PRESSURE DIFFERENTIAL STICKING AS A CONSOLIDATION PROBLEM In any borehole, where the mud pressure is higher than that exerted by the formation fluids, a mud cake is formed opposite the permeable sections of the hole and a continuous flow of filtrate takes place from the mud, through the cake and into the formation. This radial flow pattern requires a certain distribution of the hydraulic and the effective (grain-to-grain) stresses inside the mud cake. Any quantitative or qualitative change in the external pressure conditions will produce a change in the flow pattern and, consequently, also in the internal stress distribution inside the cake. In view of the low permeability and the high compressibility of a clay mud cake, the adjustment of the internal stress distribution is slow and is accompanied by a change in volume. Time dependent stresses are thus created which gradually diminish as the new state of equilibrium between internal and external pressures is approached. Some 30 years ago, Terzaghi developed his "Theory of Consolidation" to account for the time-dependent stresses and settling of clay formations under the influence of external loads. He derived a differential equation by which the time-dependent hydraulic stress and the consolidation can be computed for any point inside the layer during the consolidation process. His theory is based on the assumption that the change in stress is solely due to a change in water content and it may only be applied to one-dimensional consolidation phenomena. Other investiga-tors5,10 have expanded his theory to include processes of more than one dimension. The difference between the external pressures on the mud cake before and after sticking is a qualitative one (isolation of part of the cake by the static contact with the drill collars after pipe movement has been stopped)&apos;, and the time-dependent stresses thus created may be investigated by means of Terzaghi&apos;s theory. By this analysis the changes in the nature of the contact surface between the drill collars and the mud cake during the sticking can be explained; and the friction force between the two may be computed as a function of the sticking time, the borehole dimensions and the mud cake characteristics.

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,&apos; coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.&apos;. &apos; In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k&apos;s from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..&apos; and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young&apos;s modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen&apos;s5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By J. Lewis, J. Harper, M. F. Ashby

A grain boundary in a metal interacts with second-phase particles, which exert a pinning force (first estimated by Zener) on the boundary opposing its motion. We have computed the shape of boundaries which interact with more or less spherical second-phase particles and have constructed a soap-film model to reproduce the shape of the boundary surface. An important result is that measurement of this shape allows the pressure, or driving force, on the boundary to be measured. We hare applied this technique to grain boundaries in two alloys and hate measured the pinning force exerted by single second-phase jwrticles on the boundaries. It is in good agreement with Zener&apos;s estimate. J\. boundary between two grains, or two bulk phases, interacts with small inclusions or particles of a second phase, whether they are gas or solid. This interaction means that the boundary, forced to migrate by a difference in free energy between the material of the two grains or phases which it separates, exerts a force on a particle which it touches, tending to drag it forward. (The movement of inclusions through metals under the influence of this force, has, in fact, been observed. 1-3) Equally, the particle can be thought of as exerting a pinning force on the boundary, tending to hold it back. Zener (in a celebrated private communication4) first realized that this interaction, and the resulting pinning force, existed. His calculation of its magnitude was crude but adequate: a spherical inclusion of radius r blanks off an area nr2 of the boundary on which it sits; since the boundary has an energy of rMM x per unit area, the blanlung-olf decreases the energy of the system by MM: this energy is returned to the system if the boundary is pulled free from the inclusion— a forward movement of the boundary by a distance r will do this—so that the maximum pinning force is Trrym.M- A similar argument can be made for inter-phase boundaries. The nature of the particle itself did not enter this, or two subsequent treatments.5,6 When it is considered, tic leifthe energyoftheb a) The boundary may enter and pass through the particle if the energy of the boundary is lower within the particle than in the matrix. Fig. l(r/). Certain coherent precipitate particles behave like this. h) More usually, the boundary will bend round the particle, enveloping and bypassing it. Fig. l(b). In doing so, it changes the structure and energy of the interface between the particle and its matrix. This means that the boundary does not touch the particle surface at right angles, as early treatments assumed,5&apos;9 but at some angle a which depends on this change in surface energy of the particle, and can be calculated from the equilibrium of surface tensions. Most precipitate particles and inclusions behave like this. Gas bubbles or liquid drops can be regarded as belonging to either group. The progress of bypassing is conveniently measured by the angle shown in Fig. 1. When the nature of the particle is ignored, its maximum pinning force is exerted when - 45 deg. When it is considered, this critical value of is found to depend on a and thus on the nature of the particle. The maximum pinning force lies between nryMM and 2jtjMM (Appendix 1). not very different from Zener&apos;s result. In reality, a boundary between crystals has a specific energy and tension which varies with the orientation of the boundary. Furthermore, recent experiments7 indicate that such a boundary is not atom-ically smooth, but has steps on it: migration of the boundary corresponds to the sweeping of these steps across the boundary surface, like the Frank model of crystal growth from the vapor. This means that the interaction of a boundary with particles should really be considered in terms of the way in which particles hinder the movement of these steps. To suppose a grain boundary or interphase boundary to be smooth, and to ignore the variation of its energy with orientation, is to liken it to a soap film. The advantage of this soap film approximation, which we have used throughout this paper, is that interaction energies and boundary shapes can be calculated easily. We have done this by numerical computation and by using a soap film model, and have compared the results with grain boundaries in an aluminum-based and a copper-based alloy. It turns out that the shape of the boundary which bulges between particles allows the pressure an it to be calculated; that is, the local driving force an the boundary can be measured. This has allowed us to check the Zener relationship experimentally.

Jan 1, 1970

By T. H. Alden

Using alternating tension-compression straining, the hardening of magnesium oxide single crystals was studied up to large stresses and strains. At 0.25 pct plastic strain amplitude, the hardening curve is approximately linear with slope 25,000 psi from the shear yield stress, 7 to 8000 psi, to 35,000psi. Above this stress, the slope decreases. The strain hardening behavior of MgO is considered qualitatively similar to that of metal single crystals. The relatively high stress attainable by strain hardening is associated apparently with the high yield stress on the cross-slip system, (001) <110>. Cleavage fracture during testing is uncommon. It is argued that the centers of high internal stress at glide band intersections, at which cracks tend to nucleate, are dispersed by cyclic strain. Special features of the glide band structure produced by cyclic strain and revealed by dislocation etch pits, support this view. Strain hardened MgO has mechanical properties greatly superior to the as-received material: yield stress, greater than 100,000 psi; elongation to fracture about 1 pct. A material is said to strain harden if the yield stress increases with an increment of plastic strain. This definition is usually applied for straining done in one direction, but is also applicable when the strain direction is periodically reversed, Fig. 1. For certain metal single crystals, data are available which permit a comparison of the hardening behavior for cyclic straining and for tension straining.&apos;-4 With certain qualifications, these data show that the same processes of hardening are operative in each type of test.5 Despite this fact, the importance of the technique is not immediately evident, although tension-compression studies of the common metals appear to suggest some deficiencies in theories of strain hardening developed exclusively on the basis of tensile tests. However, a recent observation suggests that the cyclic straining method may be very useful for studying semibrittle crystals in which large plastic strains are not accessible in unidirectional testing. The observation is that zinc crystals, when strained in tension-compression at -52°C, do not fail by cleavage at low stress (-500 psi)6 as they do in tension, but harden to a limiting stress of more than 5000 psi over a total plastic strain of about 600 pct.2 An important characteristic of the behavior of zinc crystals is the high stress, relative to the yield stress, attainable by strain hardening. By comparison, the hardening of aluminum single crystals tested by an identical technique saturates at 1100 psi. This difference is best explained by the cross-slip hypothesis of dynamic recovery.7,8 In zinc, cross slip is difficult because of the high yield stress for glide on planes other than the basal plane in the < 1120 > zone. The present work was undertaken in order to test whether these methods and ideas are applicable to other materials. Magnesium oxide single crystals, in common with most crystals of the rock-salt structure, deform plastically but fail by cleavage after a small strain when tested in tension. It was hoped that larger strains would be attained using tension-compression. There is, in addition, evidence 8a which shows that slip on the probable cross system, (001) < 110>, is difficult in magnesium oxide; it may therefore be possible to attain high stresses by strain hardening. 1) EXPERIMENTAL PROCEDURE Experimental methods used in this study were based in part on techniques reported in papers of Stokes, Johnston, and Li.&apos; MgO blocks, purchased from Norton Co., were used without further annealing. Specimens were cleaved to dimensions approximately 0.125 in. sq and 1 in. in length. The gage section, formed by chemical polishing, was sprinkled with 280 mesh silicon carbide particles in order to introduce fresh dislocations. The crystals were then cemented into cylindrical aluminum adapters and clamped in an Instron testing machine. One of two alternating straining programs was used. In the first, total cross-head travel was established and increased in steps after various numbers of cycles. In the second, a capacitance gage was used to directly measure the elongation of the specimen and the crosshead was controlled so as to keep the plastic strain amplitude constant. The straining was always symmetrical with respect to the initial, zero strain condition. While both procedures produce strain hardening, only the latter permits a measure of the total plastic strain so that hardening curves may be drawn. Constant plastic strain amplitude tests were done

Jan 1, 1963

By J. M. W. Mackenzie, C. J. Wood

In attempting to describe the size classification performance of a hydrocyclone, most workers have elected to use either an equilibrium orbit theory or an non-equilibrium orbit theory. The equilibrium orbit theory has been used by the majority of workers including Lilge,&apos; Bradley; and Yoshioka and Hotta. In applying this theory, it is argued that particles in the body of a hydrocyclone attain an equilibrium radial position where the drag force on the particle resulting from the inward radial fluid velocity is balanced by the outward centrifugal force caused by the tangential component of fluid flow. When considered over the full height of the hydrocy-clone, attainment of this radial equilibrium orbit results in the particle following a conical equilibrium envelope. It is then argued that if this envelope lies outside the envelope of "zero vertical velocity," the particle will report to the underflow, while if the equilibrium envelope lies inside the envelope of "zero vertical velocity," the particle will report to the overflow or vortex finder product. The d50-sized particle which reports in equal quantities to the underflow and overflow is assumed to correspond to particles whose equilibrium envelope is coincident with the envelope of "zero vertical velocity." In considering the equilibrium orbit theory, it is apparent that the horizontal position of the particles in the feed inlet pipe should have no effect on their ultimate destination on the hydrocyclone. Each particle should attain an equilibrium position which depends on the density, size, and shape of the particle; the density and viscosity of the fluid; and the flow patterns within the hydrocy-clone. The nonequilibrium orbit or unsteady state theory has been largely developed by Rietema4 and Mizrahi.6 Mizrahi has listed four main objections to the equilibrium orbit theory. These objections center on the short residence time in the hydrocyclone, the fact that the experimental classification curve is much less sharp than is theoretically predicted, and the absence of negative efficiency conditions in hydro cyclones operating on a feed material which is much finer in size than d50. Proponents of the nonequilibrium orbit theory argue that for a particle to discharge with the underflow it must have sufficient outward radial velocity to reach the downward-flowing region close to the hydrocyclone wall in which the flow lines are parallel to the wall and the ratio of vertical to radial velocity is constant. It is then postulated that a d50 particle entering the cyclone at the center of the feed inlet will just reach this downward-flowing region as it reaches the apex. Thus for uniform distribution of particles across the feed inlet, half the d50 particles—that is, those injected in the half of the inlet area nearest the cyclone wall —will report to the underflow while those injected in the other half will not reach the downward-flowing region and will be carried inward to the center of the cyclone and thus report in the overflow. The exact thickness of the down-ward-flowing region of fluid adjacent to the outer wall of the hydrocyclone is uncertain but Mizrahi considers it to be equal to the apex radius minus the air core radius. Particles larger than d50 have a greater outward centrifugal force acting on them than the d50 particles and may reach the wall even if injected at a distance from the wall greater than Di/2 (Di is inlet diameter). Conversely, particles smaller than d50 may not reach the wall even if injected at a distance less than Di/2 from the cyclone wall. Since the equations put forward by the proponents of both theories yield approximately the same values of d50, it is not possible to decide between these theories by measurement of d50. It should be possible however to examine the theories by injecting a small stream of solids into the feed inlet of a hydrocyclone running on clear water. If the efficiency or classification curve is measured for various horizontal injection positions, then the curves should be coincident if the equilibrium orbit theory holds. If, however, the unsteady state theory describes the cyclone operation, then the classification curves should show finer d50 sizes for particles injected close to the cyclone wall. Experimental A 6-in.-diam hydrocyclone with geometry as in Figs. 1 and 2 was used. Quartz particles were injected as a 50% by wt pulp via an 1/8-in. steel probe. For each in-

Jan 1, 1971